Background technology:
Graphene is intensive by one deck, the carbon atom that is wrapped on the honeycomb crystal lattice forms, it is typical two-dimensional nano material, the thickness of this Graphene crystal film only has 0.335nm, only be 100,000 of hair/, this special construction has contained abundant and novel physical phenomenon, make Graphene show many excellent properties, it is the highest material of intensity on the present the known world, to make up other dimension carbonaceous material (such as the zero dimension soccerballene, the one dimension carbon nanotube, three-dimensional graphite) elementary cell, in water and organic solvent, have good solvability through the later mono-layer graphite of chemistry functional, be conducive to its Uniform Dispersion and forming process.At present, most study is the macromolecular material that Graphene strengthens.
Hyperbranched polymer (hyperbranched polymer, HBP) is the emerging macromolecular material of a class, and it is the random multi-level branched polymkeric substance of height that a class has three-dimensional spherical three-dimensional arrangement.Hyperbranched polymer is the macromole of " nucleocapsid " structure, " shell " of molecule is highly branched, the a large amount of active function groups of terminal gathering, nothing is tangled between the molecule, therefore show the property that many pure type polymkeric substance are not had, such as good solubility, low solution viscosity, high reaction activity.
Resins, epoxy is a kind of thermosetting resin, the organic high molecular compound that contains two or more epoxide groups in the general reference molecule, molecular structure is to contain the active epoxide group that can react to be its feature in molecular chain, makes them can form with polytype solidifying agent generation crosslinking reaction insoluble, the not molten cancellated superpolymer of three-dimensional that has.Can obtain the curing network of high-sequential, deep-crosslinked after the curing.Its cured article has the aspect performances such as excellent machinery, heat, electricity, light, particularly dimensional stability, thermotolerance, the relative ordinary epoxy resin of shock resistance improve greatly, the differently-oriented directivity dielectric properties are excellent, in large-scale integrated microelectronic packaging material, aerospace matrix material, generator insulating material, daily electrical home appliance and the fields such as car paint, civil construction bonding adhesive and metal electrophoretic paint against corrosion, military and national defense important potential application foreground arranged.
Although it is a variety of that the method for present modified epoxy has, major part all operation technological process is complicated, has contamination phenomenon, and cost is higher, and the concept of introducing hyperbranched polymer also never was used when utilizing the Graphene modified epoxy.
Summary of the invention
The method that the purpose of this invention is to provide a kind of Hyperbranched Polymer with Terminal Amido grafted graphene oxide modified synergic Resins, epoxy, the raw material of the method is easy to get, and on the graphene oxide lamella successful grafting Hyperbranched Polymer with Terminal Amido, realized the structural mutual supplement with each other's advantages of graphite oxide and Hyperbranched Polymer with Terminal Amido, and can good Toughening Modification of Epoxy.
Concrete steps are as follows:
(1) in the 250ml beaker, adds 0.1 ~ 1g graphite oxide and 50 ~ 200ml distilled water, under ultrasonic environment, disperse 10 ~ 50min, form homodisperse graphene oxide liquid mixture;
(2) take by weighing 5 ~ 25ml triethylene tetramine, place the 250ml there-necked flask that agitator, thermometer, prolong and dropping funnel are housed, add N, dinethylformamide stirs so that triethylene tetramine just all till the dissolving, be warming up to 55 ~ 65 ℃ of mixed solutions that slowly drip 1 ~ 10mL methyl methacrylate and 1 ~ 10mL methyl alcohol, time for adding is 1.5~2.5 hours, continue to be warming up to 80~120 ℃, reacted 6~10 hours, and can obtain the transparent Hyperbranched Polymer with Terminal Amido HBP-NH of faint yellow sticky shape
2Then add 1~10mL graphene oxide liquid mixture and 1 ~ 10g NaOH, and adjusting pH value is 5 ~ 10, under 80 ~ 120 ℃ of conditions, continued ultra-sonic dispersion 2 ~ 8 hours, be cooled to room temperature after steaming methyl alcohol, strengthen water gaging and make the product precipitation, decompress filter, product absolute ethanol washing 2 ~ 3 times, obtain black powder after the drying, be the Hyperbranched Polymer with Terminal Amido grafted graphene oxide;
(3) getting the Hyperbranched Polymer with Terminal Amido grafted graphene oxide that 0.5 ~ 5g step (2) makes joins in 10 ~ 100g epoxy resin-base, decompression is bled, add again 5 ~ 25g4,4 '-diaminodiphenylsulfone(DDS), pour into after mixing in the steel die that scribbles estersil, curing molding under 120 ℃/2h+160 ℃/2h+180 ℃/2h namely makes the cured article of grafted by super branched polymer graphene oxide modified epoxy;
Described graphite oxide is take the chemical pure crystalline flake graphite as raw material, adopts the Hummers oxidation style to make;
Described distilled water, triethylene tetramine, methyl methacrylate, methyl alcohol, dehydrated alcohol, NaOH and 4,4′ diaminodiphenyl sulfone, DMF are analytical pure; Resins, epoxy is CYD-128, is technical grade.
Present method adopts cheap raw material, and simple building-up process is prepared a kind of Hyperbranched Polymer with Terminal Amido grafted graphene oxide, is used for Toughening Modification of Epoxy, has the following advantages:
(1) raw material sources of preparation graphite oxide extensively, cheap are easy to get, processing ease, technique be simple, pollution-free.
(2) on the graphene oxide lamella successful grafting Hyperbranched Polymer with Terminal Amido, realized the structural mutual supplement with each other's advantages of graphene oxide and Hyperbranched Polymer with Terminal Amido.
(3) graphene oxide/Hyperbranched Polymer with Terminal Amido can fine dispersion in epoxy resin-base, and good consistency is arranged, and Resins, epoxy is had obvious toughening modifying effect.
(4) its impact property of Resins, epoxy through this graphene oxide/Hyperbranched Polymer with Terminal Amido modification improves 2 ~ 3 times than pure epoxy resin, and tensile strength improves 40 ~ 60%, and flexural strength increases by 60 ~ 80%, and the thermolysis starting temperature improves 10 ~ 30 ℃.
(5) preparation technology is fairly simple, and certain reduction is arranged aspect cost, is conducive to industrial practical application on extensive.
Embodiment
The main raw material graphite oxide is take crystalline flake graphite as raw material, adopts the Hummers oxidation style to make, and crystalline flake graphite is chemical pure; Distilled water, triethylene tetramine, methyl methacrylate, methyl alcohol, dehydrated alcohol, NaOH and 4,4′ diaminodiphenyl sulfone, DMF are analytical pure; Resins, epoxy is CYD-128, is technical grade.
Embodiment 1:
(1) in the 250ml beaker, adds 0.5g graphite oxide and 200ml distilled water, under ultrasonic environment, disperse 30min, form homodisperse graphene oxide liquid mixture.
(2) take by weighing the 10ml triethylene tetramine, place the 250ml there-necked flask that agitator, thermometer, prolong and dropping funnel are housed, add N, dinethylformamide stirs so that triethylene tetramine just all till the dissolving, be warming up to 60 ℃ of mixed solutions that slowly drip 2.3mL methyl methacrylate and 5.0mL methyl alcohol, time for adding is 2 hours, continues to be warming up to 100 ℃, reacted 8 hours, and can obtain the transparent Hyperbranched Polymer with Terminal Amido HBP-NH of faint yellow sticky shape
2Then add graphene oxide liquid mixture and 8g NaOH that 5mL step (1) makes, and adjusting pH value is 7, under 100 ℃ of conditions, continued ultra-sonic dispersion 6 hours, be cooled to room temperature after steaming methyl alcohol, strengthen water gaging and make the product precipitation, decompress filter, product absolute ethanol washing 3 times, obtain black powder after the drying, be the Hyperbranched Polymer with Terminal Amido grafted graphene oxide.
(3) getting the Hyperbranched Polymer with Terminal Amido grafted graphene oxide that 0.26g step (2) makes joins in the 26g epoxy resin-base, decompression is bled, add again 7.8g4,4 '-diaminodiphenylsulfone(DDS), pour into after mixing in the steel die that scribbles estersil, curing molding under 120 ℃/2h+160 ℃/2h+180 ℃/2h namely makes the cured article of modifying epoxy resin through amino-terminated hyperbranched polymer-grafted graphene oxide.
Resins, epoxy after this Hyperbranched Polymer with Terminal Amido grafted graphene oxide (consumption only is the 1wt% of Resins, epoxy) modification, shock strength is brought up to 34.6kJ/m by original 14.5kJ/m2
2, the thermolysis starting temperature improves 18 ℃.
Embodiment 2:
(1) in the 250ml beaker, adds 0.5g graphite oxide and 200ml distilled water, under ultrasonic environment, disperse 30min, form homodisperse graphene oxide liquid mixture.
(2) take by weighing the 10ml triethylene tetramine, place the 250ml there-necked flask that agitator, thermometer, prolong and dropping funnel are housed, add N, dinethylformamide stirs so that triethylene tetramine just all till the dissolving, be warming up to 60 ℃ of mixed solutions that slowly drip 2.3mL methyl methacrylate and 5.0mL methyl alcohol, time for adding is 2 hours, continues to be warming up to 100 ℃, reacted 8 hours, and can obtain the transparent Hyperbranched Polymer with Terminal Amido HBP-NH of faint yellow sticky shape
2Then add graphene oxide liquid mixture and 8g NaOH that 5mL step (1) makes, and adjusting pH value is 7, under 100 ℃ of conditions, continued ultra-sonic dispersion 6 hours, be cooled to room temperature after steaming methyl alcohol, strengthen water gaging and make the product precipitation, decompress filter, product absolute ethanol washing 3 times, obtain black powder after the drying, be the Hyperbranched Polymer with Terminal Amido grafted graphene oxide.
(3) getting the Hyperbranched Polymer with Terminal Amido grafted graphene oxide that 0.78g step (2) makes joins in the 26g epoxy resin-base, decompression is bled, add again 7.8g4,4 '-diaminodiphenylsulfone(DDS), pour into after mixing in the steel die that scribbles estersil, curing molding under 120 ℃/2h+160 ℃/2h+180 ℃/2h namely makes the cured article of modifying epoxy resin through amino-terminated hyperbranched polymer-grafted graphene oxide.
Resins, epoxy after this Hyperbranched Polymer with Terminal Amido grafted graphene oxide (consumption only is the 3wt% of Resins, epoxy) modification, shock strength is brought up to 42.7kJ/m by original 14.5kJ/m2
2, the thermolysis starting temperature improves 19 ℃.
Embodiment 3:
(1) in the 250ml beaker, adds 0.5g graphite oxide and 200ml distilled water, under ultrasonic environment, disperse 30min, form homodisperse graphene oxide liquid mixture.
(2) take by weighing the 10ml triethylene tetramine, place the 250ml there-necked flask that agitator, thermometer, prolong and dropping funnel are housed, add N, dinethylformamide stirs so that triethylene tetramine just all till the dissolving, be warming up to 60 ℃ of mixed solutions that slowly drip 2.3mL methyl methacrylate and 5.0mL methyl alcohol, time for adding is 2 hours, continues to be warming up to 100 ℃, reacted 8 hours, and can obtain the transparent Hyperbranched Polymer with Terminal Amido HBP-NH of faint yellow sticky shape
2Then add graphene oxide liquid mixture and 8g NaOH that 5mL step (1) makes, and adjusting pH value is 7, under 100 ℃ of conditions, continued ultra-sonic dispersion 6 hours, be cooled to room temperature after steaming methyl alcohol, strengthen water gaging and make the product precipitation, decompress filter, product absolute ethanol washing 3 times, obtain black powder after the drying, be the Hyperbranched Polymer with Terminal Amido grafted graphene oxide.
(3) getting the Hyperbranched Polymer with Terminal Amido grafted graphene oxide that 1.3g step (2) makes joins in the 26g epoxy resin-base, decompression is bled, add again 7.8g4,4 '-diaminodiphenylsulfone(DDS), pour into after mixing in the steel die that scribbles estersil, curing molding under 120 ℃/2h+160 ℃/2h+180 ℃/2h namely makes the cured article of modifying epoxy resin through amino-terminated hyperbranched polymer-grafted graphene oxide.
Resins, epoxy after this Hyperbranched Polymer with Terminal Amido grafted graphene oxide (consumption only is the 5wt% of Resins, epoxy) modification, shock strength is brought up to 40.5kJ/m by original 14.5kJ/m2
2, the thermolysis starting temperature improves 16 ℃.
Embodiment 4:
(1) in the 250ml beaker, adds 0.5g graphite oxide and 200ml distilled water, under ultrasonic environment, disperse 30min, form homodisperse graphene oxide liquid mixture.
(2) take by weighing the 10ml triethylene tetramine, place the 250ml there-necked flask that agitator, thermometer, prolong and dropping funnel are housed, add N, dinethylformamide stirs so that triethylene tetramine just all till the dissolving, be warming up to 60 ℃ of mixed solutions that slowly drip 2.3mL methyl methacrylate and 5.0mL methyl alcohol, time for adding is 2 hours, continues to be warming up to 100 ℃, reacted 8 hours, and can obtain the transparent Hyperbranched Polymer with Terminal Amido HBP-NH of faint yellow sticky shape
2Then add graphene oxide liquid mixture and 8g NaOH that 5mL step (1) makes, and adjusting pH value is 7, under 100 ℃ of conditions, continued ultra-sonic dispersion 6 hours, be cooled to room temperature after steaming methyl alcohol, strengthen water gaging and make the product precipitation, decompress filter, product absolute ethanol washing 3 times, obtain black powder after the drying, be the Hyperbranched Polymer with Terminal Amido grafted graphene oxide.
(3) getting the Hyperbranched Polymer with Terminal Amido grafted graphene oxide that 1.82g step (2) makes joins in the 26g epoxy resin-base, decompression is bled, add again 7.8g4,4 '-diaminodiphenylsulfone(DDS), pour into after mixing in the steel die that scribbles estersil, curing molding under 120 ℃/2h+160 ℃/2h+180 ℃/2h namely makes the cured article of modifying epoxy resin through amino-terminated hyperbranched polymer-grafted graphene oxide.
Resins, epoxy after this Hyperbranched Polymer with Terminal Amido grafted graphene oxide (consumption only is the 7wt% of Resins, epoxy) modification, shock strength is brought up to 34.7kJ/m by original 14.5kJ/m2
2, the thermolysis starting temperature improves 19 ℃.